Deep Red to Near‐Infrared Emitting Rhenium(I) Complexes: Synthesis,Characterization, Electrochemistry,Photophysics, and Electroluminescence Studies

A series of triarylamine‐containing tricarbonyl rhenium(I) complexes, [BrRe(CO)₃(N^N)] (N^N=5,5′‐bis(N,N‐diaryl‐4‐[ethen‐1‐yl]‐aniline)‐2,2′‐bipyridine), has been designed and synthesized by introducing a rhenium(I) metal center into a donor‐π‐acceptor‐π‐donor structure. All of the complexes showed an intense broad structureless emission band in dichloromethane at around 680–708 nm, which originated from an excited state of intraligand charge transfer (³ILCT) character from the triarylamine to the bipyridine moiety. Upon introduction of the bulky and electron‐donating pentaphenylbenzene units attached to the aniline groups, the emission bands were found to be red shifted. The nanosecond transient absorption spectra of two selected complexes were studied, which were suggestive of the formation of an initial charge‐separated state. Computational studies have been performed to provide further insight into the origin of the absorption and emission. One of the rhenium(I) complexes has been utilized in the fabrication of organic light‐emitting diodes (OLEDs), representing the first example of the realization of deep red to near‐infrared rhenium(I)‐based OLEDs with an emission extending up to 800 nm.     

Dolphin biosonar signals measured at extreme off-axis angles: Insights to sound propagation in the head

Biosonar signals radiated along the beam axis of an Atlantic bottlenose dolphin resemble short transient oscillations. As the azimuth of the measuring hydrophones in the horizontal plane progressively increases with respect to the beam axis the signals become progressively distorted. At approximately ±45°, the signals begin to divide into two components with the time difference between the components increasing with increasing angles. At ±90° or normal to the longitudinal axis of the animal, the time difference between the two pulses measured by the hydrophone on the right side of the dolphin's head is, on average, ～11.9?μs larger than the time differences observed by the hydrophone on the left side of the dolphin's head. The center frequency of the first pulse is generally lower, by 33-47?kHz, than the center frequency of the second pulse. When considering the relative locations of the two phonic lips, the data suggest that the signals are being produced by one of the phonic lips and the second pulse resulting from a reflection within the head of the animal. The generation of biosonar signals is a complex process and the propagation pathways through the dolphin's head are not well understood.     

A density functional study on nitrogen-doped carbon clusters CnN3- (n=1-8)

Using molecular graphics software, we designed numerous models of CnN3- (n=1-8). Geometry optimization and calculation on vibration frequency were carried out by the B3LYP density functional method. After comparison of structure stability, we found that the structures of ground-state CN3- and C2N3- are bent chains with a nitrogen atom at either end, whereas when n=3-8, the ground-state clusters show three branches, each with a nitrogen atom located at the end. When n=5-8, the longest branch of CnN3- is polyacetylenelike. When n=5 or 7, the longest branch is connected to the central sp2 carbon in a nonlinear manner. The CnN3- (n=1-8) with an even number of carbon atoms are more stable than those with odd numbers, matching the peak pattern observed in laser-induced mass spectra of CnN3-. The trend of such odd/even alternation is explained based on concepts of bonding characteristics, electron affinities, and incremental binding energies.     

A new angle on pluronic additives: advancing droplets and understanding in digital microfluidics

Biofouling in microfluidic devices limits the type of samples which can be handled and the duration for which samples can be manipulated. Despite the cost of disposing fouled devices, relatively few strategies have been developed to tackle this problem. Here, we have analyzed a series of eight amphiphilic droplet additives, Pluronic coblock polymers of poly(propylene oxide) (PPO) and poly(ethylene oxide) (PEO), as a solution to biofouling in digital microfluidics using serum-containing cell culture media as a model fluid. Our analysis shows that species with longer PPO chains are superior for enabling droplet motion and reducing biofouling. Two of the tested species, L92 and P105, were found to lengthen device lifetimes by 2-3 times relative to additives used previously when used at optimal concentrations. Pluronics with low PEO content such as L92 were found to be cytotoxic to an immortalized mammalian cell line, and therefore we recommend that Pluronic additives with greater or equal to 50% PEO composition, such as P105, be used for digital microfluidic applications involving cells. Finally, contact angle measurements were used to probe the interaction between Pluronic-containing droplets and device surfaces. Strong correlations were found between various types of contact angle measurements and the capacity of additives to reduce biofouling, which suggests that contact angle measurements may be useful as a tool for rapidly screening new candidates for the potential to reduce biofouling. We propose that this study will be useful for scientists and engineers who are developing digital microfluidic platforms for a wide range of applications involving protein-containing solutions, and in particular, for applications involving cells.     

Thermal Decomposition of Ternary Sodium Graphite Intercalation Compounds

Graphite intercalation compounds (GICs) are often used to produce exfoliated or functionalised graphene related materials (GRMs) in a specific solvent. This study explores the formation of the Na-tetrahydrofuran (THF)-GIC and a new ternary system based on dimethylacetamide (DMAc). Detailed comparisons of in situ temperature dependent XRD with TGA-MS and Raman measurements reveal a series of dynamic transformations during heating. Surprisingly, the bulk of the intercalation compound is stable under ambient conditions, trapped between the graphene sheets. The heating process drives a reorganisation of the solvent and Na molecules, then an evaporation of the solvent; however, the solvent loss is arrested by restacking of the graphene layers, leading to trapped solvent bubbles. Eventually, the bubbles rupture, releasing the remaining solvent and creating expanded graphite. These trapped dopants may provide useful property enhancements, but also potentially confound measurements of grafting efficiency in liquid-phase covalent functionalization experiments on 2D materials.     

Matsuoka—Nakai与Lade-Duncan两破坏准则之间的相互关系

Matsuoka-Nakai和Lade-Duncan两种破坏准则在三维主应力空间中均满足外凸、连续、光滑等条件,能正确描述中间主应力对岩土类材料的区间强度效应.本文首先从理论上探讨了Lade-Duncan和Matsuoka-Nakai两个破坏准则之间的相互联系,证明了Lade-Duncan 破坏准则的kL合理范围应在[kMinL,kMaxL]之间,指出了其在e平面上的投影形状是多样的.其次结合砂土的真三轴强度破坏的实验资料,验证了Lade-Duncan和Matsuoka-Nakai两个破坏准则之间的相互关系,认为Lade-Duncan破坏准则的kL在[kMinL,kAveL]范围内能对岩土类材料的抗剪强度给出良好地描述.     

A data mining framework for product and service migration analysis

With new technologies or products invented, customers migrate from a legacy product to a new product from time to time. This paper discusses a time series data mining framework for product and service migration analysis. In order to identify who migrate, how migrations look like, and the relationship between the legacy product and the new product, we first discuss certain characteristics of customer spending data associated with product migration. By exploring interesting patterns and defining a number of features that capture the associations between the spending time series, we develop a co-integration-based classifier to identify customers associated with migration and summarize their time series patterns before, during and after the migration. Customers can then be scored based on the migration index that integrates the statistical significance and business impact of migration customers. We illustrate the research through a case study of internet protocol (IP) migration in telecommunications and compare it with likelihood-ratio-based tests for change point detections.     

Inexact subgradient methods with applications in stochastic programming

In many instances, the exact evaluation of an objective function and its subgradients can be computationally demanding. By way of example, we cite problems that arise within the context of stochastic optimization, where the objective function is typically defined via multi-dimensional integration. In this paper, we address the solution of such optimization problems by exploring the use of successive approximation schemes within subgradient optimization methods. We refer to this new class of methods as inexact subgradient algorithms. With relatively mild conditions imposed on the approximations, we show that the inexact subgradient algorithms inherit properties associated with their traditional (i.e., exact) counterparts. Within the context of stochastic optimization, the conditions that we impose allow a relaxation of requirements traditionally imposed on steplengths in stochastic quasi-gradient methods. Additionally, we study methods in which steplengths may be defined adaptively, in a manner that reflects the improvement in the objective function approximations as the iterations proceed. We illustrate the applicability of our approach by proposing an inexact subgradient optimization method for the solution of stochastic linear programs.This work was supported by Grant Nos. NSF-DDM-89-10046 and NSF-DDM-9114352 from the National Science Foundation.     

A note on the derivation of filter regularization operators for nonlinear evolution equations

Despite the strong focus of regularization on ill-posed problems, the general construction of such methods has not been fully explored. Moreover, many previous studies cannot be clearly adapted to handle more complex scenarios, albeit the greatly increasing concerns on the improvement of wider classes. In this note, we rigorously study a general theory for filter regularized operators in a Hilbert space for nonlinear evolution equations which have occurred naturally in different areas of science. The starting point lies in problems that are in principle ill-posed with respect to the initial/final data – these basically include the Cauchy problem for nonlinear elliptic equations and the backward-in-time nonlinear parabolic equations. We derive general filters that can be used to stabilize those problems. Essentially, we establish the corresponding well-posed problem whose solution converges to the solution of the ill-posed problem. The approximation can be confirmed by the error estimates in the Hilbert space. This work improves very much many papers in the same field of research.     

Approximation of an Inverse Initial Problem for a Biparabolic Equation

In this paper, we consider the problem of finding the initial distribution for the linear inhomogeneous and nonlinear biparabolic equation. The problem is severely ill-posed in the sense of Hadamard. First, we apply a general filter method to regularize the linear nonhomogeneous problem. Then, we also give a regularized solution and consider the convergence between the regularized solution and the sought solution. Under the a priori assumption on the exact solution belonging to a Gevrey space, we consider a generalized nonlinear problem by using the Fourier truncation method to obtain rigorous convergence estimates in the norms on Hilbert space and Hilbert scale space.